Sesamolyl ethers and thioethers

ABSTRACT

Novel ethers, thioethers and amines having an oxo-substituted chain and the ketal thereof for the control of insects.

United States Patent 1 1 1111 3,723,467

Siddall et al. I 1 Mar. 27, 1973 I54] SESAMOLYL ETHERS AND [56] References Cited THIOETHERS UNITED STATES PATENTS [75] Inventors: John B. Siddall; Clive A. Henrick,

both of Palo Alto, Calif 3,563,932 2/[97] BOWCI'S ..260/340.5

[73] Assignee: Zoecon Corporation, Palo Alto, OTHER PUBLICATIONS Calif.

Bowers, Science," Vol. 164 (3877), 1969, pp. [22] Filed: Nov. 12, 1970 323425 [21] App]. No.: 89,022

Primary Examiner-Alex Maze] A J d 52 U.S. c1. ..260/340.5,260/340.9,260/470, fig g fg 'ggzg' l zi'g 260/47] R, 260/473 C, 260/473 R, 260/488 y CD, 260/516, 260/518 R, 260/518 A, 260/519, 260/521 R, 260/521 A, 260/571, [571 ABSTRACT 2605761260590, Novel ethers, thioethers and amines having an 0x0- 424/282 substituted chain and the ketal thereof for the control 51 1111.131. ..C07d 13/10 insect, [58] Field of Search ..260/340.5

l 1 Claims, No Drawings SESAMOLYL ETHERS AND THIOETHERS This invention relates to novel oxo-substituted ethers, thioethers and amines, intermediates therefor and the control of insects.

The novel compounds of the present invention having an oxo-substituted aliphatic chain and the ketal thereof useful for the control of insects are represented by the following formulas:

n is zero or a positive integer of one to four;

R is oxygen atom or cycloethylenedioxy;

each of R and R is hydrogen or lower alkyl having a chain length of one to five carbon atoms;

each of R and R is hydrogen or lower alkyl having a chain length of one to six carbon atoms;

R is lower alkyl having a chain length of one to six carbon atoms;

W is oxygen atom or sulfur atom;

R is one of the groups 3,4-methylenedioxyphenyl, 4- alkylcarbonylphenyl, 4-formylphenyl, 4-alkoxycarbonylphenyl, 4-carboxyphenyl, phenyl 3,4- dinitrophenyl, 2,4-dinitrophenyl, 4-nitrophenyl, 2-

' lower alkoxy-4-nitrophenyl, 2-halo-4-nitrophenyl, 2-lower alkyl-4,6-dinitrophenyl, 2,3 or 4- monohalophenyl, 2,4-dihalophenyl, 3,4- dihalophenyl, 2,3-dihalophenyl, 2,4,6-trihalophenyl, 2-lower alkoxy-4-halophenyl, 4-lower alkoxy, 2,4-di(lower)-alkoxy, 3,4-di(lower)alkoxy, 2-or 4- lower alkylphenyl, 2,4- or 2,6-di(lower)alkylphenyl, 4-nitrosophenyl, 2,4-dinitrosophenyl, 4-lower alkylthiophenyl, 2,4-di-lower alkylthiophenyl or 4- lower alkylthio-S-lower alkylphenyl, said halo is bromo, chloro or fluoro; and

R is hydrogen, lower alkyl or the same oxo-substituted aliphatic chain or ketal thereof.

The term alkyl, as used herein, refers to a straight or branched chain saturated aliphatic hydrocarbon group having achain length of one to 12 carbon atoms, such as methyl, ethyl, n-p'ropyl, i-propyl, n-butyl, nhexyl, n-amyl, n-heptyl, n-octyl, n-nonyl, lauryl, ndecyl, t-amyl, 3-ethylpentyl and 2-methylhexyl. The term lower alkyl, as used herein, refers to a primary or secondary alkyl group, branched or straight chain. The term lower alkyl, however, when used in defining the group R includes tertiary alkyl groups.

The compounds of formula A, B, C and D, including the cycloethylene ketals, are useful for the control of insects. The utility of these compounds as insect control agents is believed to be attributable to their juvenile hormone activity. They are preferably applied to the immature insect, namely during the embryo, larvae or pupae stage in view of their ability to inhibit metamorphosis and otherwise cause abnormal development. These compounds are effective control agents for Hemipteran insects, such as Lygaeidae, Miridae and Pyrrhocoridae; Lepidopteran insects, such as Pyralidae, Noctiidae and Gelechiidae; and Coleopteran; such as Tenebrionidae; and Dipteran. The compounds can be applied at low dosage levels of the order of 0.001 pg. to 15.0 p.g. per insect. Suitable carrier substances include liquid or solid carriers, such as water, mineral or vegetable oils, talc, vermiculite, natural and synthetic resins and silica. Treatment of insects in accordance with the present invention is accomplished by spraying, dusting or exposing the insects to the vapor of the compounds of formula A, B, C and D. Generally, a concentration of less than 25 percent of the active compound is employed. The formulations can include insect attractants, emulsifying agents or wetting agents to assist in the application and effectiveness of the active ingredient.

In the description following and hereinafter, each of m, m', n, R, R, R R, R, R R, R and W is as defined hereinabove and X is bromo or chloro.

The ethers, thioethers and amines of formulas A, B, C and D of the present invention can be prepared from the bromide or chloride of formulas ,V and VI.

The compounds of formulas A and B, that is the ethers and thioethers, are prepared by the reaction of a chloride or bromide of formula V or VI with an alcohol (HO-R or a thiol (HS-R The reaction is generally carried out in an organic solvent inert to the reaction, such as methanol, ethanol, acetone, dimethylformamide, dioxane, dimethoxyethane, ether, tetrahydrofuran or dimethylacetamide in the presence of a base, such as an alkali metal hydride, alkali metal salts and alkaline earth metal salts, e.g., sodium hydride, sodium carbonate, potassium carbonate, sodium hydroxide, potassium hydroxide, and the like. The compounds of formulas C and D are prepared by the reaction of a chloride or bromide of formula V or V1 with a primary or secondary amine of the formula:

V w H N- R wherein R and R are as defined above. In the case of a primary amine (R is hydrogen), the reaction yields a mixture of monosubstituted amine and di-substituted amine (i.e., R being the same oxo-substitutecl aliphatic chain or ketal thereof). The mixture can be separated by chromatography.

The precursors of formulas V and V1 are prepared according to the following outlined synthesis.

in o

in the practice of the above-outlined synthesis, a saturated ketone of formula 11 is reacted with an aldehyde (R -CH -CHO) using Aldol conditions to yield the unsaturated ketone (111). A ketone of formula 111 is then alkylated using an organocopper complex wherein the organo group is R'-CH=Cl-l-(CH,),,, formed from cuprous salt and organo-lithium or organo-magnesium halide to yield the ketone (IV). Preparation of organo-copper complexes is described by House et al., J. Org. Chem. 34, 3615 (1969), Siddall et al., J. Am. Chem. Soc. 91, 1853 (1969) and H002 et al., Canadian J. Chem. 48, 1626 (1970). The bromides and chlorides of formula V are prepared by the reaction of a ketone of formula IV (R is hydrogen) with hydrogen bromide or hydrogen chloride in the presence ofa free radial initiator, such as an organic peroxide or ultraviolet radiation. This free radical addition can be done in the presence or absence of a solvent and over a wide temperature range depending upon the initiator and olefin (IV). A good description of free radical addition of hydrogen bromide and hydrogen chloride to olefins and references is provided by Organic Reactions, Vol. 13, pages 162-164 and 233-234 (1963). Conversion of the ketone (1V) into the alcohol (lV) is carried out by reaction with mercuric salt in the presence of water followed by treatment with sodium borohydride as described in our application Ser. No. 78,908, filed Oct. 7, 1970. The alcohol (lV) is then treated with a halogenating agent, such as phosphorus tribromide, phosphorus trichloride, or the like, to yield the corresponding halide (VI). Preparation of the ketones (II) is described in our application Ser. No. 78,908, the disclosure of which is incorporated by reference. The cycloethylene ketals of the present invention are prepared by treatment of a ketone (R is an oxygen atom) with ethylene glycol in organic solvent, such as toluene, in the presence of acid catalyst, such as ptoluenesulfonic acid.

The following examples are provided to illustrate the practice of the present invention. Temperature is given in degrees Centigrade.

EXAMPLE 1 A. To 19 g. of cuprous iodide in 40 ml. of ether, 20 under nitrogen, is added ml. of ethylmagnesium bromide (3M) and 20 ml. of ether. After about 20 minutes, 10 g. of mesityl oxide in 10 m1. of ether is added slowly. The reaction is allowed to proceed until starting material disappears as indicated by vapor phase chromatography. The mixture is poured into iced ammonium chloride solution and extracted with ether. The ether extracts are washed until neutral and evaporated to yield 4,4-dimethylhexan-2-one which is purified by distillation.

The foregoing procedure is repeated using each of methylmagnesium bromide, n-propylmagnesium bromide, i-propylmagnesium bromide and n-butylmagnesium bromide in place of ethylmagnesium bromide to yield 4,4-dimethylpenta-2-one, 4,4-dimethylheptan-2- one, 4,4,S-trimethylhexan-Z-one and 4,4-dimethyloctan-2-one, respectively.

B. 40 Milliliters of n-butyl lithium (1.6M in hexane) is added slowly to a stirred solution of 13 ml. of bis(trimethylsilyl) amide in 20 ml. of ether and refluxed for 30 minutes. Tetrahydrofuran (10 ml.) is then added to form a solution of lithium bis( trimethylsilyl)amide.

To 5 g. of 4,4-dimethylhexan-2-one in 4 ml. of tetrahydrofuran, 78 under nitrogen, is added slowly 50 ml. of the above solution. After about 10 minutes, 5 g. of propionaldehyde is added slowly. After about 30 minutes at -78", the reaction is allowed to rise to 0. The mixture is extracted with ether and the ether extracts washed with water and brine. Fractional distillation with vigreux column yields 7,7-dimethylnon-3-en- S-one.

The foregoing process is repeated using each of the other quaternary alkyl ketones of Part A as the starting material to yield 7,7-dimethyloct-3-en-5-one, 7,7- dimethyldec-3-en-5-one, 7,7,8-trimethylnon-3-en-5- one and 7,7-dimethylundec-3-en-5one, respectively.

C. To 2.5 g. of magnesium in 20 ml. of ether, under nitrogen, is added a crystal of iodine and 5 drops of lbromopent-4-cnc. When the reaction starts, there is then added additional 1-bromopent-4-ene for a total of grams. After about 0.5 hour, temperature is lowered to 30 and cuprous iodide (19g) is added. Reaction mixture is left until negative Gilman test obtained and 1 1 g. of 7,7-dimethylnon-3-en-5-one is added. About 5 minutes after addition is complete, the mixture is poured into ice-cold ammonium chloride and after 1 hour, extracted with ether. The ether extracts are washed, dried and evaporated to yield 6-ethyl-l0,l0- dimethyldodec-l-en-S-one which is purified by distillation.

The foregoing process is repeated using each of the unsaturated ketones of Part B as the starting material to yield 6-ethyl-10, lO-dimethylundecl -en-8-one, 6- ethyl-lO,10-dimethyltridec-l-en-8-one, 6-ethyll 0, 1 0, 1 1 -trimethyldodec- 1 -en-8-one and 6-ethyl- 1 0, l O-dimethyltetradecl -en-8-one, respectively.

D. To 3.2 g. of mercuric acetate in 10 ml. of water is added 10 ml. of tetrahydrofuran followed by 2.2 g. of 6- ethyl-l0,IO-dimethyldodec-l-en-S-one in a few ml. of tetrahydrofuran. The mixture is stirred about 45 minutes and then 10 ml. of 10 percent sodium hydroxide is added followed by 10 ml. of a solution of 400 mg. of sodium borohydride in 10 ml. of 10 percent sodium hydroxide. After addition is complete, mixture is stirred five minutes and allowed to stand several hours at 5. The layers are separated and ether backwash of water layer combined with organic layer. The organic phase is dried over magnesium sulfate and evaporated to yield 6-ethyl-10,lO-dimethyl-8-oxododecan-2-ol which can be purified by distillation.

By use of the foregoing procedure, each of the unsaturated ketones of Part C is converted into the corresponding hydroxyl compound, namely 6-ethyl-8- oxo- 1 0, l 0-dimethylundecan-2-ol, 6-ethyl-8-oxo- 10,10- dimethyltridecan- 2-01, 6-ethyl8-oxo-l0,IO-trimethyldodecan-2-ol and 6-ethy1-10,10-dimethy1-8-oxotetradecan-Z-ol.

EXAMPLE 2 A. By use of the procedure of Example 1 (A), each of but-3-en-2-one, pent-3-en-2-one and hept-3-en-2- one, as the starting material, is converted into hexan-2- one, 4-methylhexan-2-one and 4-ethylheptan-2-one, respectively.

B. Each of saturated ketones of Part A is used as the starting material in the procedure of Example 1 (B) to yield non-3-en-5-one, 7-methylnon-3-en-5-one and 7- ethyldec-3-en-5-one, respectively, which are used as the starting material in the process of Example 1 (C) to yield 6-ethyldodecl -en-8-one, 6-ethyll O-methyldodec'1-en-8-one and 6, lO-diethyltridec-1-en-8-one, respectively.

C. Each of the 8-keto compounds of Part B is subject to the process of Example 1 (D) to yield 6-ethyl-8-oxododecan-2-ol, 6-ethyl- 1 0-methy1-8-oxododecan-2-ol and 6, 1 O-diethyl-8-oxotridecan-2ol.

EXAMPLE 3 Propionaldehyde is reacted with 5,5-dimethylhexan- 2-one using the process of Example 1 (B) to yield 8,8- dimenthylnon-B-en-S-one which is used as the starting material in the process of Example 1 (C) to yield 6- ethyl-l1,1l-dimethyldodec-1-en-8-one. The thus-obtained l-en-8-one compound is threated with mercuric acetate followed by sodium borohydride to yield 6- ethyl-l 1 ,1 l-dimethyldodecan-Z-ol.

EXAMPLE 4 A. Each of the saturated ketones 4,4-dimethylhexan-2-one, 4,4-dimethylpentan-2-one, 4,4-dimethylheptan-2-one, hexan-2-one, 4-methylhexan-2-one, 4-ethylheptan-2-one and 5,5-dimethylhexan-2-one is reacted with acetaldehyde using the procedure of Example 1 (B) to yield the corresponding unsaturated ketone i.e., 6,6-dimethyloct-2-en-4-one, 6,6-dimethylhept-2- en-4-one, 6,6-dimethylnon-2-en-4-one, oct. 2-en-4- one, 6-methyloct-2-en-4-one, 6-ethylnon-2-en-4-one and 7,7-dimethyloct-2-en-4-one, respectively.

B. The thus-obtained unsaturated ketones of Part A are used as the starting material in the procedure of Example 1 (C) to yield the corresponding 1-en-8-keto compounds namely, 6,10,10-trimethyldodec-l-en-8- one, 6,10,10-trimethylundec-1-en-8-one, 6,10,10- trimethyltridec- 1 -en-8-one,6-methyldodecl-en- 8-one, 6, 1 O-dimethyldodec- 1f tridec-l-en-8-one and 6,11,11-trimethyldodec-1-en-8- one, respectively.

C. Each of the 8-oxo compounds of Part B is reacted with mercuric acetate followed by sodium borohydride using the procedureof Example 1 (D) to yield the cor responding C-2 alcohol-namely, 6,10,10-dimethyl- 8-oxododecan-2-ol, 6,10, l0-trimethyl-8-oxo-undecan- 2-01, 6,l0,lO-trimethyl-8-oxotridecan-2-ol, 6methyl-8- oxododecan-2-ol, 6,10-dimethyl-8-oxododecan-2-ol, 6- methyl-lO-ethyltridecan-Z-ol and 6,11,11-trimethyl-8- oxododecan-2-ol, respectively.

Each of the unsaturated ketones of Example 4 (A) is reacted with the Grignard of l-bromobut-3-ene according to the procedure of Example 1 (C) to yield 5 ,9,9-dimethylundec len-7-one, 5 ,9,9-trimethyldec 1- en-7-one, 5,9,9-trimethyldodec-l-en-7-one, 5- methylundec-1-en-7-one, 5 ,9-dimethy1undec-1-en-7- one, 5-methyl-9-ethyldodec-1-en-7-one and 5,10,10- trimethylundec-l-en-7-one, respectively. Each of the thus-obtained l-en-7-one compounds is used as the starting material in the process of Example 1 (D) to yield 7-oxo5,9,9-trimethylundecan-2-ol, 7-oxo-5,9,9- trimethyldecan-Z-ol, 7-oxo-5,9,9-trimethyldodecan-2- o1, 7-oxo-5-methylundecan-2-ol, 7-oxo-5 ,9- dimethylundecan-2-ol, 7oxo-5-methyl-9-ethyldodecan- 2-ol and 7-oxo-5,10,10-trimethylundecan-2-ol, respectively.

EXAMPLE 6 A. Each of the unsaturated ketones of Example 4 (A) is reacted with the Grignard of 1-bromohex-4-ene using the procedure of Example 1 (C) to yield 7,1 1,1 1- trimethyltridec-2-en-9-one, 7,1 1,11-trimethyldodec-2- en-9-one, 7,1 1,1 1-trimethyltetradec-2-en-9-one, 7- methyltridec-2-en-9-one, 7,1 l-dimethyltridec-2-en-9- one, 7-methyll 1 -ethyltetradec-2-en-9-one and 7 l 2, l 2-trimethyltridec-2-en-9-one, respectively.

B. Each of the ketones obtained in Part A is reacted with mercuric acetate followed by sodium borohydride to yield a mixture of 7,1 1,1 l-trimethyl-9-oxotridecan-3 -ol and 7,1 l,l-trirnethyl-9-oxotridecan-241 -ol; 7,1 1,1l-trimethyl-9-oxododecan-3-ol and 7,1 1,1 1- trirnethyl-9-oxododecan-2-ol; 7 ,1 1,1 1-trimethyl-9-oxotetradecan-3-ol and 7,1 1,1 1-trimethyl-9-oxotetradecan-Z-ol; 7,1l-dimethyl-9-oxotridecan-3-ol and 7,1l-dimethyl-9-oxotridecan-Z-ol; 7-methyl-llethyl-9-oxotetradecan-3-ol and 7-methyl-ll-ethyl-9- oxotetradecan-2-ol; and 7,l2,l2-trimethyl-9-oxotridecan-B-ol and 7,l2,12-trimethyl-9-oxotridecan-2- ol, respectively, each mixture is separated by chromatography to yield the individual C-3 alcohol and C-2 alcohol.

EXAMPLE 7 A. To a mixture of 10 g. of 6-ethyl-10,10-dimethyl-8- oxododecan-Z-ol in 50 ml. of ether at is added a solution of 6 ml. of phosphorus tribromide in 25 ml. of ether slowly. The mixture is stirred for 0 for 2 hours and then heated at about 30 for 2 hours. The mixture is cooled, washed with water, dried over magnesium sulfate and evaporated to yield 2-bromo-6-ethyl-l0,l0- dimethyldodecan-8-one.

By using phosphorus trichloride in the foregoing procedure, the corresponding chloride is obtained.

Using the process of this example, each of the alcohols of Examples 1 to 6 is converted into the corresponding bromide and chloride. For example, each of 2-bromo-6-ethyl,10-methyldodecan-S-one, 2-bromo- 6,l0-diethyltridecan-8-one, 2-bromo-6,l0,l0- trimethyltridecan-8-one and 2-bromo-5,9-dimethylundecan-7-one is obtained from 8-oxo-6-ethyl-l0-methyldodecan-Z-ol, 8-oxo-6,l0-diethyltridecan-2-ol, 8-oxo- 6,10,lO-trimethyltridecan-Z-ol and 7-oxo-5,9- dimethylundecan-Z-ol, respectively.

B. To a solution of 2 g. of 4-nitrophenol in 10 ml. of dimethylformamide is added 2 g. of potassium carbonate and 5 g. of 2-bromo-6-ethyl-10,10-dimethyldodecan-8-one, the reaction mixture is heated at about 45 for 10 hours. The mixture is then diluted with water and extracted with ether. The ethereal extract is washed with aqueous potassium hydroxide and water, dried over sodium sulfate and evaporated under reduced pressure to yield 1-(6'-ethyl-8-oxo-l0',l0- dimethyldodecan-Z'-yloxy)-4-nitrobenzene.

EXAMPLE 8 To a mixture of l g. of sodium and 30 ml. of methanol at room temperature is added 5 g. of methyl p-hydroxyphenyl ketone and then 8 g. of 2-bromoethyl-l0,l0-dimethyldodecan-8-one. The mixture is then refluxed for eight hours. After cooling, the mixture is diluted with water and then extracted with ether. The ethereal extract is washed, dried over magnesium sulfate and evaporated to yield methyl 4-(6'-ethyl-8'- oxo-l0',10'-dimethyldodecan-2'-yloxy)phenyl ketone which is purified by chromatography.

EXAMPLE 9 To methanolic sodium methoxide (0.5 g. of sodium and 7 g. of absolute methanol) is added 3 g. of methyl p-hydroxybenzoate and then about 6 g. of 2-bromo-6- ethyl-l0,l0-dimethyldodecan-8-one. The mixture is refluxed for about ten hours. After cooling, the mixture is filtered and the filtrate concentrated. The concentrate is diluted with water and then extracted with ether. The ethereal extract is dried over sodium sulfate and evaporated to yield methyl 4-(6-ethyl-8-oxo-l0 ',l0-dimethyldodecan-2-yloxy)benzoate which is purified by chromatography.

EXAMPLE 10 To a suspension of l g. of sodium hydride in 10 ml. of tetrahydrofuran, under argon, cooled to 4, is added 3.38 g. of sesamol in 15 ml. of tetrahydrofuran over 1 hour followed by stirring for about 16 hours. With cooling, 6 g. of 2-bromo-6-ethyl-l0,10-dimethyldodecan-8- one in ether is added over about 1 hour. The reaction is warmed to about room temperature and left for about 16 hours. The reaction is poured into water and extracted with ether. The ethereal phase is washed with 10 percent sodium hydroxide, water and saturated sodium chloride, dried over sodium sulfate and solvent evaporated to yield l-(6'-ethyl-8'-oxo-10',l0- dimethyldodecan-2-yloxy)-3,4methylenedioxybenzene.

EXAMPLE 1 1 To a solution of 4.0 g. of 3,4methylenedioxyaniline in 20 ml. of dimethylformamide is added 10 g. of 2- bromo-6-ethyl-l0,10-dimethyldodecan-S-one and 5.0 g. of potassium carbonate. The mixture is heated at about for 8 hours. The mixture is then diluted with water and extracted with ether. The ethereal phase is washed, dried over magnesium sulfate and evaporated to yield crude N-6-ethyl-8-oxo-lO,l0-dimethyldodecan-Z-yl 3,4-methylene dioxyaniline which is purified by chromatography.

EXAMPLE 12 A. 6,6-Dimethyloct-2-en-4-one is alkylatcd using divinylcopperlithium tri-n-butylphosphine complex by the procedure of H002 and Layton, Canadian Journal of Chemistry 48, 1626 (1970) to yield 3,7,7-trimethylnonl-en-5-one.

B. A solution of 10 g. of 3,7,7-trimethylnon-l-en-5- one in about ml. of pentane in a quartz flask, partially immersed in ice water, is irradiated with a Hanovia-5-100 quartz tube mercury vapor lamp for two hours while hydrogen bormide is passed through the solution. The solution is then washed with 10 percent aqueous sodium carbonate and water and pentane evaporated to yield l-bromo-3,7,7-trimethylnonan-5- one which is purified by chromatography.

Alternatively, the C-1 bromide can be prepared by the following method.

One mole of 3,7,7-trimethylnon-l-en-5-one and about 0.8 mole percent of dibenzoyl peroxide is cooled in an ice-bath and then 1.5 moles of dry hydrogen bromide is passed in rapidly. After about 1 hour, the mixture is washed with aqueous sodium carbonate and water and dried over sodium sulfate to yield crude lbromo-3,7,7-trimethylnonan-5-one which is purified by chromatography.

The C-l chloride, i.e., l-chloro-3,7,7-trimethylnonan-S-one is obtained using hydrogen chloride in either of the foregoing procedures.

EXAMPLE 13 A. A solution of 0.5 moles of vinylithium in tetrahydrofuran is slowly added, at 78, to a solution of 0.25 mole of tetrakis[iodo-(tri-n-butylphosphin'e)copper(l)]. Then, a solution of 0.13 mole of 6,6- dimethylhept-2-en-4-one in tetrahydrofuran is added slowly, the solution allowed to warm to about 0 and allowed to stand for about 1 hour. The mixture is poured into saturated ammonium chloride solution and extracted with ether. The ethereal phase is washed, dried over sodium sulfate and solvent evaporated to yield 3,7,7-trimethyloct-l-en--one which is purified by chromatography.

By use of the foregoing process, each of 6,6- dimethyloct-2-en-4-one, 7,7-dimethylnon-3-en-5-one, 7-ethyl-7-methylnon-3-en-5-one, 6-methyloct-2-en-4- one and 7-methylnon-3-en-5-one, prepared by the procedure of Example 1 (B) is alkylated to yield 3,7,7- trimethylnon-l-en-S-one, 3-ethyl-7,7-dimethylnon-len-S-one, 3,7'diethyl-7-methylnon-1-en-5-one, 3,7- dimethylnon-l-en-S-one and 3-ethyl-7-methylnon-len-S-one, respectively. Each of the C-1 unsaturated compounds of this Example is used in the procedure of Example 12 (B) to yield the bromides under Column 1, respectively.

l-bromo-3 ,7,7-trimethyloctan-5-one, l-bromo-3 ,7,7-trimethylnonan-5-one, l-bromo-3-ethyl-7 ,7-dimethylnonan-5-one, l-bromo-3 ,7-diethyl-7-methylnonan-5-one, l-bromo-3 ,7-dimethylnonan-5-one, l-bromo-3ethyl-7-methylnonan-5-one.

EXAMPLE 14 A. To a solution of lithium diallylcuprate (0.5 mol of di-n-butylthiocuprous iodide and 1 mol of allyllithium) in ether at 78 is added 0.45 mol of 6,6-dimethyloct- 2-en-4-one in ether. The mixture is allowed to warm to 0 and then is partitioned between ether and aqueous solution of ammonia and ammonium chloride. The ether phase is washed with brine, dried and evaporated to yield crude 4,8,8-trimethyldec-l-en-6-one which is purified by chromatography.

By use of the foregoing process, each of 6,6- dimethylhept-2-en-4-on e, 7,7-dimethylnon-3-en-5-one, 7-ethyl-7-methylnon-3-en-5-one, 6-methyloct-2-en-4- one and 7-methylnon-3-en-5-one is alkylated to yield 4,8,8-trimethylnon-l-en-6-one, 4-ethyl-8,8-dimethyldec-l-en-o-one, 4,8-dimethyl-8-methyldec-l en-6-one, 4,8-dimethyldec-l6-one and 4-ethyl-8-methyldec-l -en-6-one. Each of the thus-obtained C-l unsaturated compounds is used in the process of Example 12 (B) to yield the C-1 bromides under Column 11:

l-bromo-4,8 ,8-trimethyldecan-6-one, l-bromo-4,8,8-trimethylnonan-6-one, l-bromo-4-ethyl-8 ,8-dimethyldecan-6-one, l-bromo-4,8-diethyl-8-methyldecan-6-one, 1-bromo-4,8-dimethyldecan-6-one, l-bromo-4-ethyl-8-methyldecan-6-one.

EXAMPLE 15 trimethylnonyloxy)-4-nitrobenzene which is purified by chromatography.

Similarly, using each of the bromides of Example 13 as the starting material, there is obtained l-(4'-oxo- 3,7,7-trimethyloctyloxy)-4-nitrobenzene, l-(5-oxo-3'- ethyl-7,7'-dimethylnonyloxy)-4-nitrobenzene, l-(5- oxo-3,7'-diethyl-7'-methylnonyloxy)-4-nitrobenzene, 1-(5'-oxo-3,7'-dimethylnonyloxy)-4-nitrobenzene and l-(S'3'-ethyl-7'-methylnonyloxy)-4- nitrobenzene, respectively.

By the same procedure, l-bromo-4,8,8-trimethyldecan-6-one is converted into l-(6-oxo-4',8',8'- trimethyldecyloxy)-4-nitrobenzene. Likewise, each of the bromides of Example 14 is converted into the corresponding p-nitrophenyl ether.

B. Following the procedure of Part A, each of 3,4- dinitrophenol, 2,4-dinitrophenol, 2-methoxy-4- nitrophenol, 2-ethoxy-4-nitrophenol, 2-chloro-4- nitrophenol, 2-bromo-4-nitrophenol and 2-methyl-4,6- dinitrophenol is reacted with l-bromo-3,7,7-trimethylnonan-S-one to yield the corresponding ether, that is l-(5'-oxo-3,7,7'-trimethylnonyloxy)-3,4- dinitrobenzene, l-(5-oxo-3,7,7'-trimethylnonyloxy)- 2,4-dinitrobenzene, 1-(5'-oxo-3',7',7'trimethylnonyloxy)-2-methoxy-4-nitrobenzene, l-(5-oxo-3',7', 7'-trimethylnonyloxy)-2-ethoxy-4-nitrobenzene, l-(5'- oxo-3,7,7'-trimethylnonyloxy)-2-chloro-4- nitrobenzene, l-(5'-oxo-3',7,7'-trimethylnonyloxy)-2- bromo-4-nitrobenzene and l-(5 '-oxo-3 ,7 ,7 trimethylnonyloxy)-2-methyl- 4,6-dinitrobenzene. Similarly, each of the bromides of Examples 13 and 14 is converted into the corresponding ether.

EXAMPLE 16 A. To a suspension of l g. of sodium hydride (washed with pentane) in 10 ml. of tetrahydrofuran, under argon, cooled to 4 is added 3.4 g. of sesamol in 15 ml. of tetrahydrofuran over 1 hour. The mixture is stirred for about 16 hours. With cooling in ice-bath, to the mixture is added 4.5 g. of l-bromo-3,7,7-trimethylnonan-5 -one in ether slowly. After about 2 hours, the mixture is warmed to room temperature and allowed to stand for about 16 hours. The mixture is poured into water and extracted with ether. The ethereal phase is washed with dilute sodium hydroxide, water and saturated brine, dried over sodium suflate and solvents evaporated to yield l-(5'-oxo-3,7',7'-trimethylnonyloxy)-3,4- methylenedioxybenzene which is purified by chromatography.

By use of the foregoing process, each of the bromides of Examples 13 and 14 is converted into the corresponding 3,4-methylenedioxyphenyl ether.

B. The process of Part A i repeated using phenol in place of sesamol to yield p-(5-oxo-3,7,7 trimethylnonyloxy)-benzene.

EXAMPLE 17 A. To methanolic sodium methoxide (0.5 g. of sodium and 7 ml. of methanol) at 20 is added methyl phydroxybenzoate (3 g. and then 4 g. of l-bromo- 3,7,7-trimethylnonan-5-one. The mixture is refluxed for about ten hours. After cooling, the mixture is filtered and filtrate concentrated. The concentrate is diluted with water and then extracted with ether. The ethereal phase is dried over sodium sulfate and evaporated to yield methyl trimethylnonyloxy)benzoate.

By the above process, the bromides of Example 13 and 14 are converted into the corresponding methyl benzoates.

B. The process of Part A is repeated using methyl phydroxyphenyl ketone as the starting material to yield methyl poxo- 3 ,7 ',7 trimethylnonyloxy)phenyl ketone. 1n the same manner, each of the bromides of Examples 13 and 14 is converted into the corresponding methyl p-substituted phenyl ketone. Similarly, other alkyl p-hydroxyphenyl ketones, such as ethyl phydroxyphenyl ketone, are etherified.

EXAMPLE 18 Following the procedure of Example 16, each of 4- methoxyphenol, 2,4-dimethoxyphenol, 3,4-dimethoxyphenol, 4-methylphenol, 4-t-butylphenol and 2,4- dimethylphenol is reacted with 1-bromo-3,7,7- trimethylnonan-S-one to yield the corresponding ether, that is 1-(5'-ox0-3',7,7'-trimethy1nonyloxy)-4- methoxybenzene, l-(5'-oxo-3,7,7'-trimethylnonyloxy)-2,4-dimethoxybenzene, 1-(5'-oxo-3',7',7'- trimethylnonyloxy)-3,4-dimethoxybenzene, 1-(5'-oxo- 3',7',7-trimethylnonyloxy)-4 methylbenzene, l-(5- oxo-3',7',7'-trimethylnonyloxy)-2,4-dimethylbenzene, respectively.

Similarly, the other bromides of Examples 13 and 14 are reacted with the above substituted phenols to yield the corresponding ethers.

EXAMPLE 19 Through the use of the process of either Examples 15, 16 or 17, 1-bromo-3,7,7-trimethylnonan-5-one is etherified with each of 4-chloropheno1, 2,4- dichlorophenol, 3,4-dichlorophenol, 2,3- dichlorophenol, 2,4,6-trichlorophenol, 2,3,6-

trichlorophenol, 2,4,5-trich1orophenol, 2-methoxy-4- chlorophenol, 2-methyl-4-chlorophenol, 2-chloro-4-tbutylphenol and 2-chloro-4,5-dimethylphenol to yield:

1-(5'-oxo-3',7,7-trimethylnonyloxy)-4- chlorobenzene, 1-(5'-oxo-3,7',7'-trimethylnony1oxy)-2,4-

dichlorobenzene, l-(5'-ox0-3',7',7-trimethylnonyloxy)-3,4-

dichlorobenzene, 1-(5'-oxo-3,7',7'-trimethylnonyloxy)-2,3-

dichlorobenzene, 1-(5'-oxo-3',7',7'-trimethylnonyloxy)-2,4,6-

trichlorobenzene, 1-(5-oxo-3',7',7'-trimethylnonyloxy)-2,3,6-

trichlorobenzene, 1-(5'-oxo-3',7,7'-trimethylnonyloxy)-2,4,5-

trichlorobenzene, l-(5'-oxo-3',7,7'-trimethylnonloxy)-2-methoxy-4- chlorobenzene, l-(5-oxo-3',7',7-trimethylnonyloxy)-2-methyl-4- chlorobenzene, l-(5'-oxo-3,7,7'-trimethylnonyloxy)-4-t-butyl-2- chlorobenzene and l-(5-oxo-3',7',7'-trimethylnonyloxy)-4,5-dimethyl- 2-ch1orobenzene, respectively. Similarly, each of the bromides of Examples 13 and 14 is etherified using the above substituted phenols to yield the corresponding ethers.

EXAMPLE 20 Using the process of either Example 15 or 16, 1- bromo-3,7,7-trimethylnonan-5-one is etherified with each. of 4-nitrosophenol, 2,4-dinitrosophenol, 4- methylthiophenol, 2,4-dimethylthiophenol, 4- methylthio-3-methylphenol and 4-methylthio-3,5- dimethylphenol to yield each of l-(5-oxo-3',7,7- trimethylnonyloxy)-4-nitrosobenzene, 1-(5-oxo-3',7', 7 -trimethylnonyloxy)-2,4-dinitrosobenzene, 1-(5 oxo-3,7',7-trimethylnonyloxy)-4-methylthiobenzene, 1-(5'3,7,7-trimethylnonyloxy)-2,4- dimethylthiobenzene, 1-(5'-oxo-3,7,7-trimethylnonyloxy)-4-methylthio-3-methy1benzene and 1-(5'- oxo-3,7,7-trimethylnony1oxy)-4-methylthio-3,5- dimethylbenzene, respectively. Similarly, each of the bromides of Examples 13 and 14 is etherified using the above substituted phenols to yield the corresponding ethers.

EXAMPLE 21 A mixture of 1 g. of methyl 4-(5'-oxo-3',7,7'- trimethylnonyloxy)benzoate, ml. of methanol, 0.2 g. of sodium carbonate and 6 ml. of water is stirred at about 30 for about 5 hours. The mixture is diluted with water, neutralized and then extracted with ether. The organic phase is washed with water, dried over sodium sulfate and evaporated to yield 4-(5'-oxo-3',7',7'- trimethylnonyloxy)benzoic acid.

A solution of 1 g. of 4-(5-oxo-3',7,7-trimethylnonyloxy)benzoic acid and one equivalent of diazoethane in ether is allowed to stand one hour at 0 and then at room temperature for 2 hours. The mixture is then washed with water, dried and organic phase evaporated to yield ethyl 4-(5'-oxo-3,7',7'-trimethylnonyloxy)benzoate.

EXAMPLE 22 A mixture of 5 g. of 1-bromo-3,7,7-trimethylnonan-5 -one, 1.5 equivalents of ethylene glycol and 250 mg. of p-toluenesulfonic acid monohydrate in 200 ml. of toluene is refluxed for 8 hours under Dean-Stark apparatus with continuous removal of water. The mixture is then cooled, neutralized by addition of sodium carbonate, dried over magnesium sulfate and evaporated under reduced pressure to yield l-bromo-5,S- cycloethylenedioxy-3,7,7-trimethylnonane which can be purified by chromatography.

EXAMPLE 23 To a solution of2 g. of sodium in 50 m1. of methanol at about 0 is added 35 g. of methyl p-thiobenzoate. After about 0.5 hour, about 15 g. of 1-bromo-3,7,7- trimethylnonan-S-one is added and then the mixture is refluxed for about three hours. The the solvent is evaporated and the concentrate taken up in petroleum ether which is washed with water, dried over magnesium sulfate and evaporated to yield methyl 4-(5'-oxo- 3 ',7 ,7 -trimethylnonylthio)-benzoate.

Similarly, each of the bromides of Examples 13 and 14 is used as the starting material in place of l-bromo- 3,7,7-trimethylnonan-5-one to yield the corresponding thioethers.

EXAMPLE 24 A suspension of sodium hydride in mineral oil (0.5 g., 50 percent is mixed with 15 ml. of dioxane under nitrogen and then 1.7 g. of methyl p-aminobenzoate in ml. of dioxane is added. The mixture is refluxed and then 2.4 g. of l-bromo-3,7,7-trimethylnonan-5-one in ml. of dioxane is added and the mixture refluxed for about two hours. The mixture is cooled, filtered and the filtrate concentrated. The concentrate is taken up in ether, washed with water and dilute aqueous HCl, dried over magnesium sulfate and evaporated to yield methyl N-3,7,7-trimethyl-5-oxo-nonyl-paminobenzoate which is purified by chromatography on silica.

The above process is useful for preparing the corresponding amines from the bromides of Examples 13 and 14.

By using a larger amount of the C-1 bromide reagent in the above process, the formation of tertiary amine (formulas C and D wherein R is the oxo-substituted aliphatic chain) is favored. Thus, in the above process, used of about 4.8 g. of l-bromo-3,7,7-trimethylnonan- 5-one gives almost exclusively methyl N,N-3,7,7- trimethyl'5-oxononyl-paminobenzoate.

EXAMPLE 25 To a solution of 4.0 g. of 3,4-methylenedioxyaniline in ml. of dimethylformamide is added 8.5 g. of lbromo-3,7,7-trimethylnonan-5-one and 5 g. of potassium carbonate. The mixture is heated at about 60 for 8 hours. The mixture is then diluted with water and extracted with ether. The ethereal phase is washed, dried over magnesium sulfate and evaporated to yield crude N-3,7,7-trimethyl-5-oxononyl 3,4-methylenedioxyaniline which is purified by chromotography. Similarly, the other bromides of Examples 13 and 14 are converted into the corresponding amine.

EXAMPLE 26 Following the process of either Example 24 or 25, each of 2-chloroaniline, N-methyl-3-chloroaniline, ethyl para-n-butylaminobenzoate, 2,6-dichloro-4- nitroaniline, 3,5-dichloroaniline, 3,5-dichloro-4- methylthioaniline, 3,5-dibromo-4-methylthioaniline, aniline, 4-nitroaniline, 4-methoxyaniline and 2,4- dimethylthioaniline is reacted with l-bromo-3,7,7- trimethylnonan-S-one to yield:

N-3,7,7-trimethyl-5-oxononyl 2-chloroaniline,

N,N-methyl-3,7,7-trimethyl-5-oxononyl 3- chloroaniline, ethyl N,N-n-butyl-3,7,7-trimethyl-5-oxononyl p- 2,6-dichloro-4- 3,5-dibromo-4- Similarly each of the bromides of Examples 13 and 14 are converted into the corresponding amines.

EXAMPLE 27 Using the procedure of Example 23, each of 3,4- methylenedioxyphenylmercaptan 4-chlorophenylmercaptan and phenylmercaptan is reacted with l-bromo- 3,7,7-trimethylnonan-S-one to yield 3,7,7-trimethyl-5- oxononyl 3,4-methylenedioxyphenyl sulfide, 3,7,7- trimethyl-S-oxononyl 4-chlorophenyl sulfide and 3,7,7- trimethyl-S -oxononyl phenyl sulfide.

EXAMPLE 28 Using the process of either Example 24 or 25, each of 2-methyl-6-ethylaniline, 2-isopropylaniline and 2,6- diisopropylaniline is reacted with l-bromo-3,7,7- trimethylnonan-S-one to yield N-3,7,7-trimethyl-5-oxononyl 2-methyl-6-ethylaniline, N-3,7,7-trimethyl-5- oxononyl 2-isopropylaniline and N-3,7,7-trimethyl-5- oxononyl 2,6-diisopropylaniline.

What is claimed is:

l. A compound selected from those of the formulas A or B:

m is a positive integer of one to five;

m' is a positive integer of two to five;

n is zero or a positive integer of one to four;

R is oxygen atom or cycloethylenedioxy;

each of R and R is hydrogen or lower alkyl having a chain length of one to five carbon atoms;

each of R and R is hydrogen or lower alkyl having a chain length of one to six carbon atoms;

R is lower alkyl having a chain length of one to six carbon atoms; and

W is oxygen atom or sulfur atom.

2. A compound according to claim 1 wherein each of m and m is two or three; n is zero or one; each of R and R is hydrogen or methyl; R is hydrogen, methyl or ethyl; and each of R and R is methyl or ethyl.

3. A compound according to claim 2 wherein R is oxygen atom.

4. A compound according to claim 1 wherein R is oxygen atom.

5. A compound according to formula A of claim 4 wherein R is hydrogen or methyl; IR is hydrogen, methyl or ethyl; each of R and R is methyl or ethyl; m is two or three; and n is zero or one.

6. A compound according to claim 5 wherein W is oxygen atom.

7. A compound according to claim 6 wherein m is two and n is zero.

8. A compound according to formula B of claim 4 wherein each of R and R is hydrogen or methyl; R is hydrogen, methyl or ethyl; each of R and R is methyl or ethyl; n is zero or one and m is two or three.

9. A compound according to claim 8 wherein n is 11. The compound, l-(S'-oxo-3,7',7'-trimethylzero and m is three. nonyloxy)-3,4-methylenedioxy benzene, according to 10. A compound according to claim 9 wherein W is claim 1. oxygen atom. 

2. A compound according to claim 1 wherein each of m and m'' is two or three; n is zero or one; each of R1 and R2 is hydrogen or methyl; R3 is hydrogen, methyl or ethyl; and each of R4 and R5 is methyl or ethyl.
 3. A compound according to claim 2 wherein R is oxygen atom.
 4. A compound according to claim 1 wherein R is oxygen atom.
 5. A compound according to formula A of claim 4 wherein R2 is hydrogen or methyl; R3 is hydrogen, methyl or ethyl; each of R4 and R5 is methyl or ethyl; m'' is two or three; and n is zero or one.
 6. A compound according to claim 5 wherein W is oxygen atom.
 7. A compound according to claim 6 wherein m'' is two and n is zero.
 8. A compound according to formula B of claim 4 wherein each of R1 and R2 is hydrogen or methyl; R3 is hydrogen, methyl or ethyl; each of R4 and R5 is methyl or ethyl; n is zero or one and m is two or three.
 9. A compound according to claim 8 wherein n is zero and m is three.
 10. A compound according to claim 9 wherein W is oxygen atom.
 11. The compound, 1-(5''-oxo-3'',7'',7''-trimethylnonyloxy)-3,4-methylenedioxy benzene, according to claim
 1. 